US2927880A - Dimethyl-2, 2, 2-trichloro-1-acetyloxy-ethyl phosphonate - Google Patents

Dimethyl-2, 2, 2-trichloro-1-acetyloxy-ethyl phosphonate Download PDF

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Publication number
US2927880A
US2927880A US628506A US62850656A US2927880A US 2927880 A US2927880 A US 2927880A US 628506 A US628506 A US 628506A US 62850656 A US62850656 A US 62850656A US 2927880 A US2927880 A US 2927880A
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United States
Prior art keywords
acetyloxy
trichloro
compound
dimethyl
dipterex
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Expired - Lifetime
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US628506A
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John E Casida
Arthur Belton Wayne
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Wisconsin Alumni Research Foundation
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Wisconsin Alumni Research Foundation
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Priority to US628506A priority Critical patent/US2927880A/en
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic System
    • C07F9/02—Phosphorus compounds
    • C07F9/28—Phosphorus compounds with one or more P—C bonds
    • C07F9/38—Phosphonic acids RP(=O)(OH)2; Thiophosphonic acids, i.e. RP(=X)(XH)2 (X = S, Se)
    • C07F9/40—Esters thereof
    • C07F9/4003—Esters thereof the acid moiety containing a substituent or a structure which is considered as characteristic
    • C07F9/4006—Esters of acyclic acids which can have further substituents on alkyl

Definitions

  • the novel acyloxy compound of the present invention involves the replacement of the hydroxy (OH) group at the 1-position in the ethyl group with an acyloxy, i.e. acetyloxy 5 /O (CHaC-O) group.
  • OH hydroxy
  • CHaC-O acetyloxy 5 /O
  • Example reaction mixture and the resulting aqueous mixture extracted twice with 100 ml. portions of hexane to recover the desired dimethyl-2,2,2 -trichloro-l-acetyloxyethylphosphonate.
  • the activity of the l-acetyloxy compound of the present inventon can be illustrated by tests where this compound at 1% level killed 71% of the Fowler strain of DDT and methoxychlor resistant housefiies in 24 hours when added to 100 mgm. of pyrethrins per 100ml. of refined kerosene whereas DDT at 2% in a similar test using the Patented Mar. 8 19,60
  • the l -acetyloxy compound also breaksdown under similar conditions but no toxic vinyl phosphate of this type is formed and the degradation products'are relatively nontoxic.
  • Tests with rats have also shown the mammalian toxicity of dipterex to be about double that of the l-acetyloxy compound, the median lethal doses being 400 and 950 mg./kg., respectively.
  • the reduction the mammalian toxicity to about onehalf was unexpected as the related diethyl-2,2,2-trichloro- 1acetyloxyethylphosphonate has a toxicity (about 112 mg./ kg.) of the same order as the unacetylated compound.
  • the l-acetyloxy compound of the present invention is particularly adaptable for dispensing in solution form in relatively inexpensive.
  • petroleum hydrocarbon distillates of the type used as diluents and carriers in the insecticide field. These include general house sprays, pressurized illustrative.

Description

DIIVIETI- IYL-Z JJ-TRICHLORO-l-ACETYLOXY- ETHYL PHOSPHONATE John E. Casida and Belton Wayne Arthur, Madison,
V Vrs.,- assiguors to Wisconsin Alumni Research Foundatron, Madison, Wis., a corporation of Wisconsin No Drawing. Application December 17, 1956 Serial No. 628,506
2 Claims. (Cl. 167-22) CHaO O H CH30 H It is a potent insecticide and can be used in insecticide dusts and in relatively expensive solvents such as acetone and ethylene dichloride as described in the Lorenz patent. Its use, however, has been materially restricted due to its insolubility in petroleum hydrocarbon distillates.
In the search for improved insecticides including insecticides soluble in inexpensive petroleum hydrocarbon distillates or solvents of the kerosene type, we discovered (1) that dipterex could be readily acylated, (2) that the acylated dipterex retained its potent insecticide properties and (3) that the acylated dipterex, unlike dipterex, was soluble in petroleum hydrocarbon distillates including kerosene and the like. The novel acyloxy compound of the present invention involves the replacement of the hydroxy (OH) group at the 1-position in the ethyl group with an acyloxy, i.e. acetyloxy 5 /O (CHaC-O) group. The following example is illustrative.
Example reaction mixture and the resulting aqueous mixture extracted twice with 100 ml. portions of hexane to recover the desired dimethyl-2,2,2 -trichloro-l-acetyloxyethylphosphonate. Upon removal of the solvent by evaporation the acetylated product is obtained as an oil and displays C=O absorption but no COH absorption in an infrared spectrogram.
The activity of the l-acetyloxy compound of the present inventon can be illustrated by tests where this compound at 1% level killed 71% of the Fowler strain of DDT and methoxychlor resistant housefiies in 24 hours when added to 100 mgm. of pyrethrins per 100ml. of refined kerosene whereas DDT at 2% in a similar test using the Patented Mar. 8 19,60
same amounts of pyrethrins and keroseneproduced only 59% mortality. Dipterex, being insoluble in kerosene, V
is not suitable for thisfm'ethod of application- When applied in. acetone to flies dipterex and. its acetyl derivaand in the same concentrations disclosed in the Lorenz Patent No. 2,701,225, to kill flies, roaches and the like, including DDT resistant housefiies as noted above. Unlike malathion, it is odor free and unlike dipterex, its degradation products are non-toxic. Dipterex, for example, in the presence of a trace of alkali breaks down and forms dimethyl-2,2-dich1orovinyl phosphate which is a very toxic compound. The l -acetyloxy compound also breaksdown under similar conditions but no toxic vinyl phosphate of this type is formed and the degradation products'are relatively nontoxic. Tests with rats have also shown the mammalian toxicity of dipterex to be about double that of the l-acetyloxy compound, the median lethal doses being 400 and 950 mg./kg., respectively. The reduction the mammalian toxicity to about onehalf was unexpected as the related diethyl-2,2,2-trichloro- 1acetyloxyethylphosphonate has a toxicity (about 112 mg./ kg.) of the same order as the unacetylated compound.
The l-acetyloxy compound of the present invention is particularly adaptable for dispensing in solution form in relatively inexpensive. petroleum hydrocarbon distillates of the type used as diluents and carriers in the insecticide field. These include general house sprays, pressurized illustrative. General household spray formula:
V Percent Pyrethrins 05 Technical Piperonyl butoxide 0. 10 l-acetyloxy compound 2. 0 Petroleum distillates 97. 85
Pressurized spray formula:
Pyrethrins a 0. 15 Technical piperonyl butoxide 0.50 'l-acetyloxy' compound 2. 0 Alkylated naphtha 46. Methylene chloride 5. 0 Freon 12 (CClF-fl 45. 00 Deodorized kerosene 0.6 Aerosol formula:
Pyrethrins v 25 Technical piperonyl butoxide i 1. 0 l-acetyloxy compound 2. 0 Petroleum distillates 11. 75 Propellant 1 85. 0 1 Equal quantities or Freon-11 (CCl F) and Freon-12 5 (CClzFa).
.In' the above formulations the dimethyl-2,2,2-trichloro-lacetyloxyethylphosphonate compound of the present in vention is identified by the abbreviatedterm l-acetyloxy compound. Other formulations in which the l-acetyloxy compound is applied in solution form in petroleum f 12,927,880 m r m "2. A composition in accordance with claim 1 where the FOREIGN PATENTS is'apwdeum distill? 509,034 Canada Jan. 11, 1955 4 References Cited in the file of this patent a UNITED STATES PATENTS 6 OTHER REFERENCES 2,536,647 Kosolapofi Jan. 2, 1951 Barthel ct 211.: I. Am. Chem. 800.," 77, 2424-2427 2,701,225 Lorenz Feb. 1, 1955 (1955).

Claims (1)

1. AN INSECTICIDAL COMPOSITION CONTAINING DIMETHYL2,2,2-TRICHLORO-1-ACETYLOXYETHYLPHOSPHONATE AS AN ACTIVE AGENT AND AN INSECTICIDAL CARRIER THEREFOR.
US628506A 1956-12-17 1956-12-17 Dimethyl-2, 2, 2-trichloro-1-acetyloxy-ethyl phosphonate Expired - Lifetime US2927880A (en)

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US628506A US2927880A (en) 1956-12-17 1956-12-17 Dimethyl-2, 2, 2-trichloro-1-acetyloxy-ethyl phosphonate

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US628506A US2927880A (en) 1956-12-17 1956-12-17 Dimethyl-2, 2, 2-trichloro-1-acetyloxy-ethyl phosphonate

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3070489A (en) * 1960-02-01 1962-12-25 Monsanto Chemicals Phosphinates
US3271480A (en) * 1962-05-03 1966-09-06 Bayer Ag Bis-n, nu-dialkylamino phosphoric acid esters of o, o-dialkyl-alpha-hydroxy-belta, beta, belta-trichloroethylphosphonates
US3338783A (en) * 1964-07-24 1967-08-29 Shell Oil Co Synergistic insecticidal compositions
US3445565A (en) * 1965-01-26 1969-05-20 Edmund G Locher Sprayable composition for the application to the fur of animals

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2536647A (en) * 1948-03-06 1951-01-02 Monsanto Chemicals Process of preparing bis (beta-chlorethyl)-para-nitrophenyl thiophosphate
CA509034A (en) * 1955-01-11 Dominion Rubber Company Organo-phosphorus compounds and process of making same
US2701225A (en) * 1952-09-20 1955-02-01 Bayer Ag Beta, beta, beta-trichloro-alpha-hydroxyethylphosphonic dimethyl ester and insecticidal composition thereof

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CA509034A (en) * 1955-01-11 Dominion Rubber Company Organo-phosphorus compounds and process of making same
US2536647A (en) * 1948-03-06 1951-01-02 Monsanto Chemicals Process of preparing bis (beta-chlorethyl)-para-nitrophenyl thiophosphate
US2701225A (en) * 1952-09-20 1955-02-01 Bayer Ag Beta, beta, beta-trichloro-alpha-hydroxyethylphosphonic dimethyl ester and insecticidal composition thereof

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3070489A (en) * 1960-02-01 1962-12-25 Monsanto Chemicals Phosphinates
US3271480A (en) * 1962-05-03 1966-09-06 Bayer Ag Bis-n, nu-dialkylamino phosphoric acid esters of o, o-dialkyl-alpha-hydroxy-belta, beta, belta-trichloroethylphosphonates
US3338783A (en) * 1964-07-24 1967-08-29 Shell Oil Co Synergistic insecticidal compositions
US3445565A (en) * 1965-01-26 1969-05-20 Edmund G Locher Sprayable composition for the application to the fur of animals

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